Combined slip catalyst and hydrocarbon exotherm catalyst

ABSTRACT

A catalyst comprising: (a) a first layer comprising an oxidizing catalyst having an effective PGM loading such that oxidation of hydrocarbons generates sufficient heat to regenerate soot, wherein said effective amount of PGM is greater than about 10 g/ft 3 ; and (b) a second layer adjacent to said first layer and comprising a reducing catalyst to selectively reduce NOx.

REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. patent application Ser. No.13/233,512 (pending), filed on Sep. 15, 2011, which claims priority toU.S. Provisional Patent Application No. 61/383,112, filed on Sep. 15,2010, the disclosures of both of which are hereby incorporated herein byreference in their entireties for all purposes.

FIELD OF INVENTION

The invention relates generally to emission control of lean-burnengines, and, more specifically, to a catalyst that facilitates bothexothermic oxidation of hydrocarbons and the removal ofnitrogen-containing pollutant gases from exhaust gas.

BACKGROUND

Owning to environmental concerns, there is an ever present need toreduce emissions from internal combustion engines. Of particularinterest herein are internal combustion engines operated using a leanair/fuel mixture, known as “lean-burn engines.” A common lean-burnengine is a diesel engine. The emissions in the exhaust gas of alean-burn engine can be divided into two groups—primary and secondaryemissions. Primary emissions involve pollutant gases which are formeddirectly by the combustion process of the fuel in the engine and arepresent in the raw emission before passing through exhaust gaspurification devices. The exhaust gas of lean-burn engines comprises theusual primary emissions of carbon monoxide (CO), hydrocarbons (HCs),nitrogen oxides (NOx), and soot (also known as particulate matter orPM), together with a relatively high oxygen content of up to 15% byvolume. Secondary emissions are pollutant gases which can be formed asby-products in the exhaust gas purification units. Such secondaryemissions may include, for example, “slip” ammonia (NH3) and NOx asdiscussed below.

Emission control systems have various configurations. For example,referring to FIG. 1, a typical emissions control system 100 for a dieselengine is shown. Immediately after the exhaust gas leaves the engine(not shown), a diesel oxidation catalyst (DOC) 101 oxidizes primarypollutants such as unspent fuel (hydrocarbons) and carbon monoxide torender them harmless. Other primary pollutants such as NOx cannot beoxidized, but instead must be reduced to nitrogen. Reducing NOx,however, tends to be more difficult because of the high oxygen contentin the exhaust stream.

A known method of removing NOx from exhaust gases in the presence ofoxygen is the process of selective catalytic reduction (SCR). SCR usesammonia as a reducing agent over a suitable catalyst, SCR catalyst 103as shown in FIG. 1. The reducing agent is introduced into the exhaustgas train using an injection nozzle 102. In place of ammonia, a compoundwhich can readily be decomposed into ammonia, for example, urea can beused for this purpose.

To ensure complete reduction of the NOx, ammonia has to be added to theexhaust gas in at least a stoichiometric ratio to the nitrogen oxides,and excess ammonia is preferred to improve the conversion of NOx. Excessammonia, however, significantly increases the risk of ammonia slippingpast the SCR catalyst, and becoming a secondary emission. Ammonia thatbreaks through or slips past the SCR catalyst is referred to as “slipammonia.” Since ammonia is a gas which has a penetrating odor even inlow concentrations, it is desirable to minimize slip ammonia. However,the precise metering of ammonia is difficult in internal combustionengines in motor vehicles because of the fluctuating operatingconditions of motor vehicles (e.g., acceleration/deceleration).Therefore, inevitably excess ammonia will be injected into the system,resulting in significant ammonia slip downstream of the SCR catalyst.

The system 100 also comprises a Diesel Exotherm Catalyst (DEC) 105behind the SCR 103 to facilitate periodic exothermic reactions togenerate heat sufficient to regenerate the soot from a Catalyzed SootFilter (CSF) 106. To this end, a hydrocarbon injector 104 is locatedjust upstream of the DEC. The injector 104 injects fuel or HCs into theexhaust steam when the exhaust temperature is above the DEC light-offtemperature. The DEC then oxidizes the HCs to generate an exotherm,which, in turn, heats the filter to clean the soot from it. Because theDEC is located behind the SCR, the SCR does not experience thedetrimental high temperatures associated with removing the soot.

Although the DEC is good at oxidation, it has the potential to alsounselectively oxidize any ammonia slip from the SCR catalyst and convertit to NOx, thereby increasing the NOx emissions. To counter this, oneapproach involves using an Ammonia Slip Catalyst (ASC) 201 as shown inFIG. 2. The ASC is selective for removing NH3 with minimal oxidation toNOx after the SCR catalyst 103, but in front of the HC injector 104.Typically the ASC has a low platinum group metals (PGM) loading (e.g.,0.5 to 10 g/ft3) to maximize the selectivity to N2. The disadvantage ofthis system is the additional catalyst volume required for the NH3 slipcatalyst in an already large emissions control system 200.

Therefore, Applicant recognizes the need for a simplified exhaust systemthat eliminates ammonia slip while heating the exhaust streamperiodically to regenerate soot from the soot filter. The presentinvention fulfills this need among others.

SUMMARY OF INVENTION

The following presents a simplified summary of the invention in order toprovide a basic understanding of some aspects of the invention. Thissummary is not an extensive overview of the invention. It is notintended to identify key/critical elements of the invention or todelineate the scope of the invention. Its sole purpose is to presentsome concepts of the invention in a simplified form as a prelude to themore detailed description that is presented later.

The present invention provides a combination catalyst that functions,not only to oxidize slip ammonia and hydrocarbons in an exothermicreaction sufficient to generate enough heat to regenerate soot, but alsoto reduce NOx resulting from such oxidation. More specifically,Applicant found surprisingly that the high loading concentration in theoxidation catalyst needed for generating enough heat for sootregeneration was counteracted by a SCR catalyst in immediate proximityto the oxidation catalyst. This facilitates the integration of atraditional DOC and ASC, thereby simplifying an exhaust system thateliminates ammonia slip while heating the exhaust stream periodically toregenerate soot from the soot filter.

Accordingly, one aspect of the invention relates to a combinationDOC/ASC catalyst that eliminates NH3 slip and heats the exhaust streamperiodically to regenerate soot from the soot filter, while reducingsecondary NOx emissions. In one embodiment, the combination catalystcomprises: (a) a substrate; (b) a first layer on the substrate, thefirst layer comprising an oxidizing catalyst having an effective PGMloading such that oxidation of hydrocarbons generates sufficient heat toregenerate soot, wherein, in one embodiment, the effective amount of PGMis greater than about 10 g/ft³; and (c) a second layer adjacent to thefirst layer and comprising a reducing catalyst to selectively reduceNOx.

Another aspect of the invention relates to a method of using a combinedcatalyst to heat the exhaust stream periodically to regenerate sootwhile eliminating slip ammonia and NOx emissions. In one embodiment, themethod comprises: (a) injecting a nitrogenous reductant into an exhaustflow having NOx; (b) reducing the NOx using the nitrogenous reductant inthe presence of an SCR catalyst to form a NOx-reduced gas stream, which,at least intermittently, contains slip nitrogenous reductant; (c)injecting HC into the NOx-reduced gas stream to form an HC-enriched gasstream; and (d) contacting the HC-enriched gas stream with a combinedcatalyst to form a heated gas stream, the combined catalyst comprising afirst layer having an oxidization catalyst to oxidize the slipnitrogenous reductant and the HC to heat the heated gas stream, and asecond layer having a SCR catalyst to reduce NOx formed in the firstlayer.

Yet another aspect of the invention is an exhaust system that eliminatesammonia slip while heating the exhaust stream periodically to regeneratesoot from the soot filter using a combination catalyst. In oneembodiment, the system comprises: (a) a conduit for transmitting anexhaust gas having NOx from an engine to the atmosphere; (b) an injectorfor injecting nitrogenous reductant into the exhaust gas; (c) an SCRcatalyst situated to contact the exhaust gas and reduce the NOx usingthe nitrogenous reductant to form a NOx-reduced gas stream, which, atleast intermittently, contains slip nitrogenous reductant; (d) an HCinjector for injecting HC into the NOx-reduced gas stream to form anHC-enriched gas stream; (e) a combined catalyst situated to contact theHC-enriched gas stream to form a heated gas stream, the combinedcatalyst comprising a first layer having an oxidization catalyst tooxidize the slip nitrogenous reductant and the HC to heat the heated gasstream, and a second layer having an SCR catalyst to reduce NOx in theheated gas stream; and (f) a filter disposed to contact the heated gasstream to regenerate soot contained in the filter.

BRIEF SUMMARY OF DRAWINGS

FIG. 1 shows a typical urea SCR system configuration with downstreamfuel injector.

FIG. 2 shows the SCR system of FIG. 1 with an ammonia slip catalyst(ASC) after the SCR to minimize unselective NH3 oxidation by dieselexotherm catalyst (DEC).

FIG. 3 shows an embodiment of the present invention in which the ureaSCR system configuration with downstream fuel injector comprises acombined ammonia slip catalyst and diesel exotherm catalyst.

FIG. 4 shows HC conversion for a light-off test under high hydrocarbon(exotherm) conditions for a standard DEC, a standard ASC, and a combinedDEC/SCR catalysts of the present invention.

FIG. 5 shows the performance for NH3 conversion for the same catalystsas tested with respect to FIG. 4 under low hydrocarbon conditions.

FIG. 6 shows the performance for selective conversion of NH3 to N2 forthe same catalysts as tested with respect to FIGS. 4 & 5 under lowhydrocarbon conditions.

FIG. 7 shows a schematic diagram of one embodiment of the combinationcatalyst of the present invention.

DETAILED DESCRIPTION

Referring to FIG. 3, an exhaust system 300 of the present invention isdepicted schematically. As shown, the system 300 comprises a conduit 301for transmitting an exhaust gas from an engine 307 to the atmosphere. Itis known that such exhaust streams contain NOx. Downstream of the engine307 is an injector 302 for injecting nitrogenous reductant into theexhaust flow. Following the injector 302 is a selective catalyticreduction (SCR) catalyst 303. It is situated to contact the exhaust gasand reduce the NOx using a nitrogenous reductant to form N2 andresulting in a NOx-reduced gas stream. Because the amount of NOx in theexhaust stream tends to vary considerably depending on, for example,acceleration/deceleration of the engine, operating temperatures, ambienttemperature, etc., it is difficult to maintain a precise stoichiometricbalance between nitrogenous reductant and NOx. Consequently, anabundance of nitrogenous reductant will be injected into the exhauststream, resulting in a portion of it passing through the SCR andentering the NOx-reduced gas stream. This is referred to as slipnitrogenous reductant or, more particularly, slip ammonia.

Downstream of the SCR is a hydrocarbon (HC) injector 304 for injectingHC into the NOx-reduced gas stream to form an HC-enriched stream. Acombined catalyst 305 is situated to contact the HC-enriched stream toform a heated gas stream of sufficient temperature (e.g., 400° C.) toregenerate soot contained in the catalyst soot filter (CSF) 306. Thetemperature required to regenerate soot can vary depending on theapplication. For example, typically the heated gas stream should be550-650° C., however, additives may be added to the gas stream to reducethe required temperature to about 450° C. and perhaps lower.

Referring to FIG. 7, a schematic of one embodiment of the combinedcatalyst 700 is shown. The combined catalyst 700 comprises a substrate701 upon which a first layer 702 having an oxidation catalyst isdisposed. The oxidation catalyst oxidizes the slip nitrogenous reductantand the injected HC in the HC-enriched steam. The oxidization catalysthas an effective amount of PGM (e.g., greater than 10 g/ft3) to causethe oxidation reaction to be sufficiently exothermic to heat the heatedgas stream to a suitable regeneration temperature (e.g., 400-550° C.).The catalyst 700 also comprises a second layer 703, which, in thisembodiment, overlays the first layer 702. The second layer comprises anSCR catalyst for reducing NOx in the enriched stream or generated formthe HC and nitrogenous reductant oxidation in the first layer 702.

The system, the combined catalyst, and its use are described below ingreater detail with respect to certain non-limiting embodiments.

Referring back to FIG. 3, the engine 307 may be any lean-burn type ofengine, including, for example, a diesel engine, a lean-burn gasolineengine or an engine powered by liquid petroleum gas or natural gas.

In the embodiment shown in FIG. 3, the system 300 also has a dieseloxidation catalyst (DOC) 308. The DOC 308 is a well known device thatuses a chemical process to break down pollutants in the exhaust streaminto less harmful components. More specifically, DOCs typically utilizeprecious metals catalysts to reduce the particulate matter (PM),hydrocarbon based soluble organic fraction (SOF), and carbon monoxidecontent of diesel exhaust by simple oxidation. A typical DOC is a flowthrough device comprising a canister containing a honeycomb-likestructure or substrate. The substrate has a large surface area that iscoated with an active catalyst layer. This active layer contains asmall, well dispersed amount of the precious metals. As the exhaustgases traverse the catalyst, carbon monoxide, gaseous hydrocarbons andliquid hydrocarbon particles (unburned fuel and oil) are oxidized,thereby reducing harmful emissions.

Downstream of the DOC 308 is the nitrogenous reductant injector 302,which is also well known. It serves to meter an appropriate amount ofnitrogenous reductant in to the exhaust system. Several reductants areused in SCR applications include ammonia per se, hydrazine, anhydrousammonia, aqueous ammonia or an ammonia precursor selected from the groupconsisting of urea ((NH₂)₂CO), ammonium carbonate, ammonium carbamate,ammonium hydrogen carbonate and ammonium formate. Pure anhydrous ammoniais toxic and difficult to safely store, but needs no further conversionto react with an SCR catalyst. Aqueous ammonia must be hydrolyzed inorder to be used, but it is safer to store and transport than anhydrousammonia. Urea is the safest to store, but requires conversion to ammoniathrough thermal decomposition in order to be used as an effectivereductant.

As is known, the injector 302 is controlled by a controller (not shown),which monitors a number of engine and exhaust parameters and determinesthe appropriate amount of nitrogenous reductant to inject. Suchparameters include, for example, exhaust gas NOx concentration, exhaustgas temperature, catalyst bed temperature, accelerator position, massflow of exhaust gas in the system, manifold vacuum, ignition timing,engine speed, lambda value of the exhaust gas, the quantity of fuelinjected in the engine and the position of the exhaust gas recirculation(EGR) valve and thereby the amount of EGR and boost pressure.

The SCR catalyst is also well known and typically comprises amicroporous material containing one or more transitional metals. SCRcatalysts are manufactured from various ceramic materials used as acarrier, such as titanium oxide, and active catalytic components areusually oxides of base metals (such as vanadium and tungsten), molecularsieves, such as zeolites, and various precious metals. The two mostcommon designs of SCR catalyst geometry used are honeycomb and plate.The honeycomb form usually is an extruded ceramic applied homogeneouslythroughout the ceramic carrier or coated on the substrate. Plate-typecatalysts have lower pressure drops and are less susceptible to pluggingand fouling than the honeycomb types, but plate configurations are muchlarger and more expensive. Honeycomb configurations are smaller thanplate types, but have higher pressure drops and plug much more easily.SCR catalysts suitable for use in the present invention are disclosed,for example, in molecular sieve/zeolite-based catalysts. In oneembodiment, the SCR catalyst is a transition metal-exchanged zeolite.

In the embodiment shown in FIG. 3, the SCR catalyst is upstream of thecombined catalyst 305. Such an arrangement is generally preferred(although not necessary) for engines that run intermittently such thatthe SCR 303 heats up quickly and thus reaches peak efficiency quickly.Furthermore, in this configuration, it is not exposed to the heated gasstream which can be detrimental to the SCR catalyst.

Downstream from the SCR catalyst but prior to the combined catalyst 305,an HC injector injects HC (typically fuel for the engine) into thelow-NOx gas stream to form the HC-enriched gas stream. Like thenitrogenous reductant injector, the HC injector is controlled by acontroller (not shown) which is configured to periodically cause acertain amount of HC to be injected into the stream to periodicallyregenerate soot that is captured in the CSF 306. The frequency at whichthe soot needs to be regenerated and thus the frequency and amount of HCthat needs to be injected is an optimization of the system which is wellknown to one of skill in the art.

An important aspect of the invention is the combined catalyst 305. Itcombines the functionality of an ASC 201 and a DEC 105. As mentionedabove, it was found that, while a relatively high PGM loaded oxidationcatalyst improved the oxidation of the HCs and nitrogenous reductant,the coating of SCR catalyst was surprisingly able to limit the formationof NOx. The catalyst of the invention is thus able to generatesufficient heat for soot regeneration through exothermic oxidation whileselectively oxidizing slipped ammonia.

The multi-functionality of the combined catalyst is presumably due to anumber of reactions and interactions within the combined catalyst.Without being bound to any particular theory, it is presumed that,first, NOx from the oxidation and slip ammonia from the exhaust gas areabsorbed on the second layer which is an SCR-active coating and react ina selective catalytic reaction to form water and nitrogen which desorbafter conclusion of the reaction. Here, ammonia is present in asuperstoichiometric amount. Second, slip ammonia, which has not beenused or absorbed in the SCR layer, and the HCs pass through the secondlayer to the first layer. The second layer has a powerful oxidizingaction and produced nitrogen and nitrogen oxides from the slip ammoniaand produced water, carbon dioxide and exothermal heat from the HCs. Thenitrogen formed diffuses/passes unchanged through the second layer andgoes into the atmosphere. Third, after the nitrogen oxides are formed inthe first layer, they pass through or by the SCR catalyst of the secondlayer, where they are reacted with previously-stored/slip ammonia in anSCR reaction to form N₂. Therefore, the SCR/oxidation/SCR process thatoccurs as the HC enriched gas passes through the combined catalystserves as a self regulating system in which oxidation is promoted, butover oxidation is controlled.

Referring to FIG. 7, one embodiment of the catalyst 700 is shown. Thecatalyst comprises a substrate 701, which may comprise any knownsubstrate material used in this application, including, for example,alumina. Alternatively, the catalyst may be an extruded catalyst as iswell known in the art. Furthermore, the substrate may be configured inany known configuration, including, for example, honeycomb or monolith.In one particular embodiment, the substrate is a honeycomb alumina.

As shown in FIG. 7, the first and second layers 702, 703 are configuredsuch that the second layer 703 overlays the first layer 702. It shouldbe understood, however, that other configurations are within the scopeof the invention. For example, the first and second layers may bedeposited along the substrate such that the first layer is upstream ofthe second layer. Alternatively, a series of alternating first andsecond layers may be used. Still other configurations will be obvious toone of skill in the art in light of this disclosure.

As mentioned above, the first layer comprises the oxidizing catalyst.The catalyst should be selected to ensure oxidation of the HCs andnitrogenous reductant to the extent that a significant exothermalreaction is achieved. Specifically, the exothermal reaction needs to besufficient to heat the heated gas stream to the point that it is capableof regenerating soot in the CSF 306. Generally, this will requireheating the gas to at least about 400° C. Optimum regeneration occurs atabout 550 to about 650° C. To this end, the catalyst should comprise amicroporous material, such as a zeolite or non-zeolite (e.g. alumina,ceria, zirconia, titania, or similar materials individually or incombination), sufficiently loaded with PGM to provide the desiredexotherm. Generally, the greater the PGM loading the more reactive thecatalyst.

In addition to having sufficient PGM loading to ensure adequateregeneration temperatures as described above, the PGM loading should besufficient such that the light-off temperature for exothermal generationof heat from HC is less than about 350° C. Generally, lower light-offtemperatures are desirable. If the light-off temperature is greater thanabout 350° C., then an auxiliary system may be required to heat theupstream exhaust gas. Such systems increase the complexity of theexhaust system and reduce fuel efficiency, and, thus, are generallyundesirably. Applicant has found that the temperature of the exhaust gasreaching the DEC is generally (although not necessarily) less than 350°C. Therefore, in one embodiment, the catalyst of the present inventionhas a PGM type and loading sufficient such that the catalyst light-offtemperature is less than 350° C., and, in a more particular embodiment,is less than 325° C. The preparation of the oxidation layer to providethis desired performance would be known to those of skill in the art inlight of this disclosure.

Given the need for high regeneration temperatures and a relatively lowlight-off temperature, the PGM loading required is typically greaterthan that used in traditional ASC catalysts, which tend to be less than10 g/ft3. (Loading in an ASC catalyst is typically kept relatively lowto avoid over oxidation of the slip ammonia and the generation of NOx.)Accordingly, in one embodiment, the PGM loading is greater than that oftraditional ASC catalyst. In one embodiment, the loading is greater thanabout 10 g/ft3. In another embodiment, the loading is great than about10 g/ft3 and less than about 100 g/ft3. In another embodiment, theloading is about 15 g/ft3 to about 70 g/ft3. In yet another embodiment,the loading is about 20 g/ft3.

In one embodiment, the PGM comprises palladium (Pd) and/or platinum(Pt). In another embodiment, the PGM comprises a combination of Pd andPt. Generally, Pd promotes exothermic oxidation, and Pt tends togenerate NOx from NH3. Accordingly, the relative concentrations in amixture of Pd and Pt will tend to depend on the amount of oxidationversus NOx generation desired. The relative loading of Pd to Pt may varyfrom a ratio of 1:10 to 10:1. In one particular embodiment, the PGMcomprises a combination of essentially equal portions of Pt and Pd for atotal loading of about 15-70 g/ft3.

The second layer comprises the SCR catalyst. Such catalysts are wellknown and described above with respect to SCR catalyst 303. Generally,the SCR catalyst comprises a the SCR catalyst comprising at least (i) amicroporous crystalline molecular sieve comprising; and (ii) atransition metal impregnated in the molecular sieve.

The molecular sieve may be any known or later-developed microporousstructure suitable for use as a catalyst, including zeolite andnon-zeolite sieves (as defined by U.S. Pat. No. 4,913,799 (incorporatedherein by reference)). In one embodiment, the molecular sieve comprisesat least silicon, aluminium and phosphorous and has an 8-ring poreopening structure.

In one embodiment, the molecular sieve is a silicoaluminophosphate(SAPO) molecular sieve. In one embodiment, the SAPO molecular sieveshave one or more of the following framework types as defined by theStructure Commission of the International Zeolite Association: AEI, AFX,CHA, LEV, LTA, In one embodiment, the framework type is CHA, or CHA incombination with one or more different framework types, such as, forexample, AEI-CHA intergrowths. Examples of suitable CHA SAPOs includeSAPO-34 and KYT-6. In one particular embodiment, the molecular sieve isSAPO-34. In another embodiment, the catalyst comprises two or moredifferent SAPO molecular sieves selected from the group consisting ofAEI, AFX, CHA, LEV, and LTA. In one embodiment, the zeolite has aframework type selected from AEI, AFX, CHA, LEV, LTA, BEA, MFI, FER, MORand KFI. An example of a suitable BEA zeolite is beta zeolite.

In addition to the molecular sieve, the SCR catalyst comprises atransition metal imbedded in the sieve. Suitable transition metalsinclude, for example, Cr, Mn, Fe, Co, Ce, Ni, Cu, Zn, Ga, Mo, Ru, Rh,Pd, Ag, In, Sn, Re, Ir, Au, Pr, Nd, W, Bi, Os, and Pt. In oneembodiment, the transition metal is Cu or Fe or combinations thereof. Inone embodiment, the transition metal loading is about 0.3 wt % to about10 wt % of the catalyst. The type and concentration of the transmissionmetal can vary according to sieve and the application. For example,suitable results have been achieved with SAPO-34 loaded with about 2 wt% Cu, and beta zeolite loaded with about 3 wt % Fe. Still othercombinations of sieves, transition metals and loading concentrationswill be obviousness to those of skill in the art in light of thisdisclosure.

SCR catalysts may comprise a substrate manufactured from a ceramicmaterial, such as cordierite, mullite, silica, alumina, titania, ortheir combinations. Alternatively, the substrate can be metallic. Thetwo most common substrate designs are monolith or plate and honeycomb.Plate-type catalysts have lower pressure drops and are less susceptibleto plugging and fouling than the honeycomb types, but plateconfigurations are much larger and more expensive. Honeycombconfigurations are smaller than plate types, but have higher pressuredrops and plug much more easily. Alternatively, the catalyst may be anextruded with or without a substrate. In the latter embodiment, thecatalyst has no discrete substrate. In yet another embodiment, thecatalyst is not supported at all, but is provided in bulk.

The combination catalyst 305 can be prepared using known techniques. Forexample, Canadian Application No. 2,652,837 (based on PCT PublicationNo. 2007/137675), hereby incorporated by reference, discloses a suitablepreparation procedure, although the PGM loading of the oxidation layerof the present invention needs to be higher than that disclosed in thatreference.

The heated gas leaves the combined catalyst 305 and contacts the CSF 306at which point the soot is regenerated. Such a process is well known andwill not be discussed in detail herein.

EXAMPLES

The following non-limiting examples compare five embodiments of thecombined catalyst of the present invention (samples 2-6) to aconventional DEC catalyst (sample 1) and a conventional ASC (sample 7)as set forth in Table 1 below.

TABLE 1 Sample Description 1 DEC only (no SCR layer) 35 g/ft3 Pt; 35g/ft3 Pd 2 Combined catalyst - Oxidation layer 35 g/ft3 Pt; 35 g/ft3 Pd;SCR layer beta zeolite loaded with 3 wt % Fe 3 Combined catalyst -Oxidation layer 40 g/ft3 Pt; SCR layer SAPO-34 loaded with 2 wt % Cu. 4Combined catalyst - Oxidation layer 35 g/ft3 Pt; SCR layer beta zeoliteloaded with 3 wt % Fe. 5 Combined catalyst - Oxidation layer 20 g/ft3Pt; SCR layer SAPO-34 loaded with 2 wt % Cu. 6 Combined catalyst -Oxidation layer 10 g/ft3 Pt; SCR layer SAPO-34 loaded with 2 wt % Cu. 7ASC only (no oxidizing layer) 1 g/ft3 Pt SAPO-34 loaded with 2 wt % Cu.

In these samples, the oxidation layer was prepared by preparing a wetslurry of alumina loaded with the indicated PGM at the indicatedconcentration, and then wash coating a standard ceramic honeycombsubstrate with the slurry. The SCR layer was prepared by preparing amixture of the indicated microporous material (either SAPO-34 or betazeolite) loaded with the indicated amount of Cu or Fe through ionexchange, adding a binder to the mixture, and then wash coating theoxidation layer with the mixture.

Light-Off Temperature

FIG. 4 shows the results of a light-off test (HC oxidation) at high HCconcentrations (typical for a DEC to generate an exotherm to clean afilter). This was a steady-state light-off test in an atmosphere of 12%O2, 200 ppm NH3, 200 ppm CO, 1000 ppm C10H22, 4.5% H2O, 4.5% CO2, andthe balance N2.

Although Sample 1, the conventional DEC, had the lowest light-offtemperature (<200° C.), Sample 2, the Pt/Pd combined catalyst, andSamples 3-5, the Pt combined catalysts with 20-35 wt % Pt, alsodemonstrated suitable light-off temperatures (i.e., <350° C.). Sample 6,the 10 g/ft3 Pt combined catalyst had a light-off temperature of about350° C., which is generally (although not necessarily) too high.Likewise, Sample 7, the low PGM loaded standard NH3 slip catalyst (1g/ft3 Pt) also had a light-off temperature of about 350° C. Therefore,these results indicate that a combination catalyst with suitablelight-off temperature is achieved with an oxidation layer having a PGMconcentration above 10 g/ft3.

NH3 Conversion

FIG. 5 shows NH3 conversion under standard diesel operation conditionswith low hydrocarbon concentrations (non-exotherm generation) in anatmosphere of 12% O2, 200 ppm NH3, 200 ppm CO, 100 ppm C3H6, 4.5% H20,4.5% CO2, with the balance N2. Here, all of the samples show acceptableNH3 conversion—i.e., nearly 100% NH3 conversion at about 325° C.

Selectivity

FIG. 6 shows each samples performance in selectively converting NH3 toN2. This experiment was a steady-state light-off test under the sameatmospheric conditions as in the NH3 conversion of FIG. 5. Sample 1, thestandard DEC had the lowest selectivity with a peak of 40% at relativelylow temperatures and decreasing to less than 10% with highertemperatures. Samples 2-6, the combined catalysts, had significantlybetter selectivity having a peak of about 55-70% between about 325 and425° C., which is a common operating temperature range. Samples 4 and 5,the 35 g/ft3 and 20 g/ft3 Pt combined catalysts, show particular highselectivity of about 70% between 325 and 425° C. Such selectivity iscomparable to Sample 7, a traditional ASC.

Therefore, these examples show that the combination catalyst of thepresent invention offers the benefit of good selectivity for nitrogenousreductant slip control, which can be maintained even with higher PGMloading in the oxidation catalyst for improved HC oxidation for exothermgeneration. Adding Pd to the Pt containing lower layer also improves theHC oxidation ability of the catalyst while also improving the NH3selectivity to N2.

What is claimed is:
 1. A catalyst comprising: a first layer comprisingan oxidizing catalyst having an effective PGM loading such thatoxidation of hydrocarbons generates sufficient heat to regenerate soot,wherein said effective amount of PGM is greater than about 10 g/ft³; anda second layer adjacent to said first layer and comprising a reducingcatalyst to selectively reduce NOx.
 2. The catalyst of claim 1, whereinsaid effective amount of PGM is greater than about 15 g/ft³.
 3. Thecatalyst of claim 2, wherein said effective amount of PGM is about 15g/ft3 to about 70 g/ft3.
 4. The catalyst of claim 3, wherein saideffective amount of PGM is no less than about 20 g/ft3.
 5. The catalystof claim 1, wherein said PGM is selected from the group consisting of Ptand Pd and combinations thereof.
 6. The catalyst of claim 5, whereinsaid PGM is a combination of Pt and Pd.
 7. The catalyst of claim 1,wherein said catalyst has a HC light-off temperature of less than 350°C. in an atmosphere of 12% O2, 200 ppm NH3, 200 ppm CO, 1000 ppm C10H22,4.5% H2O, 4.5% CO2, and the balance N2.
 8. The catalyst of claim 7,wherein said HC light-off temperature is no greater than about 325° C.9. The catalyst of claim 1, wherein said SCR catalyst is a molecularsieve loaded with a transition metal.
 10. The catalyst of claim 9,wherein said transition metal is selected from Cu, Fe and combinationsthereof.
 11. The catalyst of claim 10, wherein said molecular sieve is aSAPO, CHA or a beta zeolite.
 12. The catalyst of claim 1, furthercomprising a substrate upon which said first layer is disposed.
 13. Thecatalyst of claim 12, wherein said second layer overlays said firstlayer.
 14. The catalyst of claim 12, wherein said first layer isupstream of said second layer.
 15. A method of generating heat for sootremoval and reducing NH3 slip in an exhaust system, said methodcomprising: injecting nitrogenous reductant into an exhaust flow havingNOx reducing said NOx using said nitrogenous reductant in the presenceof an SCR catalyst to form a NOx-reduced gas stream, which, at leastintermittently, contains slip nitrogenous reductant; injecting HC intosaid NOx-reduced gas stream to form a HC-enriched gas stream; andcontacting said HC-enriched gas stream with a combined catalyst to forma heated gas stream, said combined catalyst comprising a first layerhaving an oxidization catalyst to oxidize at least a portion of said HCto heat said heated gas stream, and a second layer having an SCRcatalyst to reduce at least a portion of NOx in said heated gas stream.16. The method of claim 15, wherein said heated gas stream is heated toat least 400° C.
 17. The method of claim 15, wherein said HC-enrichedgas stream is less than 350° C.
 18. The method of claim 15, wherein saidfirst layer is loaded with greater than about 15 g/ft³ PGM.